WO2003046028A1

WO2003046028A1 - Composition capable of free radical polymerization resulting in shockproof organic glass materials

Info

Publication number: WO2003046028A1
Application number: PCT/FR2002/004050
Authority: WO
Inventors: Gilles Richard; Odile Primel; Leanirith Yean
Original assignee: Essilor International Compagnie Generale D'optique
Priority date: 2001-11-26
Filing date: 2002-11-26
Publication date: 2003-06-05
Also published as: FR2832717B1; EP1453874A1; US7393880B2; FR2832717A1; JP2005510594A; AU2002364405A1; US20050107537A1

Abstract

The invention concerns a composition capable of free radical polymerization comprising: a first constituent A including at least an oligomer bearing at least two functions capable of free radical polymerization and whereof the homopolymer has a glass transition temperature (Tg) less than 50 °C, said constituent being capable of resulting by polymerization in a (co)polymer having a glass transition temperature (Tg) not higher than 50 °C, preferably not higher than 0 °C and more preferably still ranging between 50 °C and 10 °C, said oligomer representing more than 15 %, preferably less than 20 % of the total weight of polymerisable monomers present in the composition; and a second constituent B including at least a (meth)acrylic monomer bearing at least a H bond promoter group, said (meth)acrylic monomer representing at least 15 % of the total weight of the polymerisable monomers and oligomers present in the composition when said monomer is a methacrylic monomer and at least 35 % of the total weight of polymerisable monomers and oligomers present in the composition when said monomer is an acrylic monomer.

Description

Radical polymerizable composition leading to impact-resistant organic glasses

The invention relates generally to photopolymerizable and / or thermally polymerizable compositions, depending on the type of initiator used for the reaction, which lead to transparent glasses, in particular ophthalmic glasses, having good impact resistance .

One of the most well-known organic glasses used for its excellent impact resistance properties is bisphenol-A polycarbonate, commonly known as PC, - and its derivatives. ^This' glass which is a thermoplastic material, is entirely satisfactory to the wearer and can be produced by injection of advantageous cost by using injection molding, well suited for mass production.

In the case of so-called prescription lenses, that is to say made on demand as a function of the correction to be made to the sight of the spectacle wearer, a semi-finished lens, previously injected and of which one of the faces already has its final geometry and the second face is surfaced, followed by smoothing and polishing operations using appropriate tools. Glasses made of impact-resistant material based on polyurethane-polyurea have recently been marketed under the brand TRIVEX ^® . The technique for obtaining such glasses is described in US Pat. No. 6,127,505.

Other materials of the same chemical family, but incorporating sulfur increasing the refractive index, are described in international patent applications WO 01 / 36.507 and WO 01 / 36.508.

These materials are obtained by polycondensation, according to a delicate process to carry out.

European patent application EP 1 035 142 describes the polymerization of an acrylic copolymer material for obtaining ophthalmic articles which comprises the polymerization of at least one α, β-ethylenically unsaturated carboxylic acid and at least one monomer of aryl (meth) acrylate in the presence of a crosslinking agent. The crosslinking agent which can represent 0.5 to 15% by weight of the total weight of the monomers present in the composition, comprises in particular ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, allyl methacrylate, 1, 3- propanediol dimethacrylate, allyl methacrylate, 1, 6-hexanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate as well as divinyl compounds including divinyl hydrocarbons and divinyl benzene.

The examples of this patent application only state the use as crosslinking agent of ethylene glycol dimethacrylate or of 1,3-butanediol dimethacrylate.

The article by Robert A. SCOTT and Nicolas A. PEPPAS “Compositional effects on network structure of highly cross-Iinked copolymers of PEG- containing multiacrylates with acrylic acid (influence of the composition on the network structure of highly crosslinked copolymers of multiacrylates containing PEG with acrylic acid) "describes a photopolymerizable composition containing PEG 400 diacrylate and 23.6% by weight of acrylic acid.

It would therefore be desirable to be able to have a composition which can be polymerized by the radical route, in particular by photopolymerization, which results in a polymer material having a high impact resistance, good thermomechanical properties, a low water absorption and which can be used. for the manufacture of transparent substrates, in particular optical articles such as ophthalmic lenses.

The above technical problems are solved according to the present invention, by a composition which can be polymerized by the radical route comprising:

- A first component A comprising at least one oligomer carrying at least two polymerizable radical functions and whose homopolymer has a glass transition temperature (T _g ) below 50 ° C, this component A being capable of leading by polymerization to a polymer having a temperature of. glass transition (T _g ) <at 50 ° C, preferably equal to or less than 0 ° C and better ranging from -50 ° C to -10 ° C, the oligomer of component A representing more than 15%, preferably at at least 20% of the total weight of the polymerizable species present in the composition; and

a second constituent B comprising at least one (meth) acrylic monomer carrying at least one promoter group of bond H, this (meth) acrylic monomer representing at least 15% of the total weight of the polymerizable species present in the composition when this monomer is a methacrylic monomer and at least 35% of the total weight of these polymerizable species when this monomer is an acrylic monomer. Preferably, the oligomer of component A is a difunctional compound. Generally, the oligomer of component A has a number-average molar mass which varies from 100 to 5000, preferably 200 to 4000, better still from 300 to 2000 g. mole ^"1 .

The oligomer of the first constituent A is preferably chosen from poly (alkylene) glycols di (meth) acrylate, bisphenol-A di (meth) acrylate polyethoxylated, oligomers dithio (meth) acrylates and urethanes di (meth) acrylates , di (meth) acrylates thioruethanes, di (meth) acrylates polysulphides.

The polyalkylene glycol .. - di (meth) acrylates * • préférés- ^are - polyethylene glycol and polypropylene glycol di (meth) acrylates, in particular polypropylene glycol di (meth) acrylates, and particularly, the polypropylene glycol dimethacrylates.

The preferred dimethacrylate oligomer is a polypropylene glycol dimethacrylate of number average molar mass of the order of 530 g. mol ^"1 (PPG 400 DMA) sold under the name SR6440P by the company CRAY VALLEY.

These polyethylene or polypropylene glycol di (meth) acrylate oligomers suitable for the present invention can be represented by the formula:

in which R ¹ and R ² represent H or CH ₃ , A represents a divalent radical of formula:

where mi, m ₂ and m ₃ are each an integer varying from 4 to 20.

When several oligomers (I) are used as a mixture, an average value can be defined: 20 m = ∑Xm.mm = 4 in which X _m is the weight ratio of the oligomer (I) for which A comprises m ethylene or propylene glycol units in its chain relative to the total weight of the oligomers of formula (I) of the mixture.

When commercial products which are already mixtures of oligomers are used as the first constituent A of the invention, this value m is easily obtained by carrying out an analysis by HPLC of the mixture t by calculating the ratio:

Sm

^X m- _Q ^û total

where S _m represents the area of the peak corresponding to the monomer (I) comprising m propylene glycol unit in the divalent radical A, and Stotai represents the total area of all the peaks corresponding to the monomers (I) for which m varies from 4 to 20.

According to the invention, mixtures of several oligomers (I) are preferably used for which the average value m as defined above varies between 5 and 10, preferably between 6 and 9.

However, it is possible to use mixtures of several oligomers (I) for which the average value is greater than 20 and preferably between 30 and 40. The calculation of the average value is carried out as above, but for l 'all the oligometric fractions, including of course for the oligomers (I) for which the value m is greater than 20. A commercial oligomer exists for A = propoxy and m = 32. More preferably, the monomers (I) have a branched structure, that is to say that the divalent radical A represents:

m ₃ having the meaning indicated above. The monomers (I) are commercially available from the company CRAY VALLEY under the trade name SR6440P, CD6440P and from the company SHIN NAKAMURA under the name 9PG and with UCB under the trade name PPG400.

SR6440P is a mixture of several monomers (I) whose central motif is:

with integer m ₃ taking the values from 3 to 10 according to the following mass ratios:, m ₃ = 3 2% m ₃ = 4 8% m ₃ = 5 14% m ₃ = 6 20% m ₃ = 7 27% m ₃ = 8 19% m ₃ = 9 9% m ₃ = 10 1%. with an average value m ₃ = 6.6.

Another class of di (meth) acrylate oligomer suitable for constituent A of composition of the invention comprises polyalkoxylated bisphenol-A dimethacrylates (preferably ethoxylated or propoxylated) having from 10 to 80 alkoxy units (in average value).

Among these bisphenol-A di (meth) acrylate compounds, mention may be made of the compounds of formula (II):

in which R ¹ and R ² represent, independently of one another, H or CH ₃ , X represents - (CH ₂ -CH ₂ -0) -, - (CH ₂ -CH ₂ -CH ₂ -0) - or - (CH ₂ -CHCH ₃ -O) -, preferably - (CH ₂ -CH ₂ -0) -, - and ni + n ₂ has an average value of 10 to 50, preferably 10 to 40.

Preferred compounds corresponding to the above formula are those for which R ¹ = R ² = CH ₃ , X = -CH ₂ CH ₂ 0 -, and ni + n ₂ = 10 or ni + n ₂ = 30.

The preferred bisphenol-A ethoxylated di (meth) acrylate oligomers are bisphenol-A dimethacrylate with 30 ethoxy units (BPA30EODMA) marketed under the names BPE-1300N by SHIN NAKAMURA CHEMICALS and SR 9036 by CRAY VALLEY, bisphenol-A dimethacrylate with 32 propoxy units, bisphenol-A diacrylate with 32 propoxy units and bisphenol-A diacrylate with 16 propoxy units.

The particularly preferred bisphenol-A oligomer is BPA30EODMA.

The oligomer of component A of the compositions of the invention can also be a di [thio (meth) acrylate], that is to say an oligomer compound containing two functions:

in particular a dithiomethacrylate corresponding to the formula:

where n is an integer from 1 to 10, or a mixture of such dithiomethacrylates.

The oligomer of component A can also be a urethane di (meth) acrylate. Mention will in particular be made of the aliphatic diacrylate urethanes marketed by the company CRAY VALLEY under the names CN934, 935, 965, 963, 966, 967, 981 and by the company UCB under the names EBECRYL 230, 244, 245, 270, 284, 285 , 4830, 4835, and 8800 and the aromatic diacrylate urethanes sold by the company CRAY VALLEY under the names CN 970, 972, 973 and 976 and the company UCB under the names EBECRYL 210, 215 and 4244.

When the oligomer of component A is a urethane di (meth) acrylate, use is preferably made of high levels of component B (at least 40% by weight of the polymerizable species present in the composition).

Component A of the compositions of the invention may also comprise at least one other comonomer, non-oligomeric, comprising at least one radical polymerizable function and preferably two radical polymerizable functions.

The preferred comonomers for component A are mono or di (meth) acrylate comonomers such as alkyl (meth) acrylates like methyl (meth) acrylate and rethyl (meth) acrylate, cycloalkyl (meth) acrylate like cycloethyl (meth) acrylate and dicyclopentyl (meth) acrylate, aryl (meth) acrylates like phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylates, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and phenoxybutyl (meth) acrylate, alkylene glycol dimethacrylate such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate.

Other comonomers include vinyl or polyvinyl compounds as well. than,. allylic or polyallylic compounds such as divinylbenzene.

However, the choice of these comonomers must be such that the first constituent A leads, by polymerization, to a polymer or copolymer having a glass transition temperature Tg equal to or less than 50 ° C.

The second constituent B is preferably a monofunctional compound and in particular a compound of formula:

CH ₂ = C (R) -Z - Z '(IV)

in which R denotes H or CH ₃ , Z represents a single covalent bond or a spacer group.

Z is preferably a divalent hydrocarbon chain, optionally interrupted by one or more heteroatoms, preferably chosen from O, S, N or by one or more groups

carbonyl C> ester C O »- O O S by one or more divalent groups chosen from:

-NH-CO-NH-

-NHCOO-

-NHCOS- -NHCSS-.

Also preferably, the hydrocarbon chain is a short chain and comprises 1 to 10 carbon atoms and better still 1 to 6 carbon atoms.

By way of example, the spacer group Z can be a polyether, polyester, polyurethane, polyurea, polythiourethane group. Z 'is a short monovalent chain, preferably comprising from 1 to 10 carbon atoms, and better still from 1 to 6 carbon atoms and comprises at least one promoter group of H bonds chosen from the groups: -COOH

-OH

-CONHR '

-NHCONHR "

-NHGOOR- - -NHCOSR ^iv

-NHR ^V in which R ', R ", R'", R ^ιv , R ^v denote, independently of each other, H or an alkyl group of 1 to 10 carbon atoms or aryl of 6 to 10 carbon atoms. The alkyl group can itself be aliphatic or cycloaliphatic.

Preferably, the alkyl group represents CH ₃ . Preferably, Z ′ represents a promoter group for binding H chosen from the groups COOH, OH and CONHR ′, preferably a group

COOH. Preferably R is a CH ₃ group.

The H-promoter group in the compound of formula

IV can also be, on its own, a carbonyl function and / or a tertiary amine function. In this case, these two functions interact with the functions previously mentioned for Z 'and which all include a polar X-H type bond (X = 0, S, N ...) to form hydrogen bonds. The carbonyl and tertiary amine functions can therefore be used in addition to the H-promoter functions previously mentioned.

The monofunctional monomers carrying preferred hydrogen bonding precursor groups are methacric acid (AMA), acrylic acid (AA) and the (meth) acrylic monoesters of dicarboxylic acids such as mono-2 (methacryloyloxy) ethylsuccinate (MA succinate) of formula:

CH ₂ = C (CH ₃ ) C0 ₂ CH ₂ CH2θ ₂ CCH ₂ CH ₂ CH ₂ CO ₂ H (a)

and mono-2- (methacryloyloxy) ethylphthalate (MA phthalate) of formula: 2- [CH ₂ = C (CH ₃ ) C0 ₂ CH ₂ CH ₂ θ ₂ C] C ₆ H ₄ CO ₂ H (b)

Preferably, component B is methacrylic acid. More preferably, the constituents A and B are only methacrylic compounds.

The compositions according to the invention also comprise a system for initiating the polymerization. The polymerization initiation system may include one or more thermal, or photochemical, polymerization initiators. These initiators are well known in the art and any conventional initiator can be used. Among the initiators of thermal polymerization which can be used in the present invention, mention may be made of peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and isopropyl peroxydicarbonate. Among the photoinitiators, mention may be made in particular of

2,4,6-trimethylbenzoyldiphenylphosphine, 1-hydroxycyclohexylephenylketone, 2,2-dimethoxy-1, 2-diphenylethane-1-one, and alkyl benzoyl ethers.

In general, the initiating agents are used in a proportion of 0.01 to 5% by weight relative to the total weight of the polymerizable monomers contained in the composition.

The polymerizable compositions according to the invention may also comprise additives conventionally used in polymerizable compositions for molding optical or ophthalmic articles, in particular spectacle glasses and lenses, in the conventional proportions, namely agents mold release, inhibitors, dyes, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds.

The advantage of using the B promoter component B is to stiffen the very flexible network formed by the component A, without however introducing too high a crosslinking density which would be detrimental to the impact resistance of the final material. Thus, the polymerized materials according to the invention have the required thermomechanical properties, namely good rigidity at 25 ° C., which is the temperature for using the glasses, and at 100 ° C., which is the temperature reached at various stages. of the glass manufacturing process and during subsequent treatments (coloring, varnishing). The materials obtained from the compositions according to the invention have an elastic modulus (E ') at 100 ° C of at least 40 MPa, preferably 100 MPa and better still at least 120 MPa, or even 150 MPa.

Preferably, the compositions according to the invention are photopolymerizable compositions and the materials obtained by polymerization of the compositions according to the invention are preferably organic glasses obtained by conventional molding, preferably by photopolymerization.

As indicated previously, the glass can be a semi-finished glass, that is to say that one of its faces remains to be surfaced to its final geometry, but of course, the method can also be applied to the manufacture of finished glass. , that is to say comprising their two optical surfaces at the desired geometry at the end of molding.

It is thus possible to obtain a finished glass as soon as possible by photopolymerization using conventional photopolymerization devices, in a manner much easier to implement and to control than in the case of polycondensation.

The glasses obtained have excellent impact resistance and very low water absorption.

The following examples illustrate the present invention. In the examples, unless otherwise indicated, all the percentages and parts are by weight.

Example 1

60 g of BPA30EODMA are mixed with 40 g of methacrylic acid at room temperature. Mixed, 0.1 g CGI 819 ^® (phosphine oxide photoinitiator from Ciba). The composition is obtained in a room with controlled lighting in a smoked glass bottle.

The composition thus prepared is poured into a mold in two parts of mineral glass previously cleaned with soda, assembled in parallel by a Barnier adhesive tape and spaced two millimeters apart. The casting takes place as follows:

- the composition is withdrawn using a sterile syringe (20 ml);

- We partially disassemble the adhesive tape to create an opening;

- insert the tip of the syringe into the opening;

- The composition is injected into the mold; and - the adhesive tape is replaced to seal the mold. The filled mold is then placed in a photochemical polymerization oven consisting of two UV.prima lamps (mercury lamps) placed on either side, and at an equal distance from the parts of the mold, the mold receiving an illumination from each lamp. about 40 milliwatts for 30 seconds.

The infrared measurements make it possible to follow the conversion of the (meth) acrylic double bonds as a function of the UV irradiation time. After 30 seconds of irradiation, the conversion is complete.

After polymerization, the adhesive tape is removed. The glasses are then removed from the mold and then checked with an arc lamp.

A final annealing at 120 ° C. makes it possible to perfect the polymerization and to relax the residual stresses of the substrate obtained.

The results are shown in Table I below:

Comparative Examples C1 and Examples 2 to 4. Example 1 is repeated while varying the proportions of methacrylic acid and BPA 30EODMA. The proportions of the starting constituents as well as the results are indicated in Table I below.

Comparative example C1 comprises as the only polymerizable monomer BPA30EODMA.

BOARD

1. ZELECUN (lubricant from DUPONT CHEMICALS) 2. UV 541 1: 2- (2-hydroxy-5'-t-octylphenyl) benzotriazole from the company AMERICAN CYANAMID. 3. CGI 819 ^® from the company CIBA GEIGY.

(The quantities of release agent, UV absorber and photopolymerization initiator are indicated in% relative to 100 parts by weight of constituents A and B.)

The starting molecule BPA30EODMA (BPE-1300N from Shin Nakamura Chemical) is a bifunctional compound whose homopolymer is very flexible (Tg = -30 ° C measured by differential scanning calorimetry).

The stiffening of the network is illustrated by the increasing values of E '(25 ° C), E' (100 ° C) and Tg during the introduction of methacrylic acid. From 50% methacrylic acid, the Tg obtained is greater than 150 ° C. which is particularly high for a thermoset acrylic network.

The density of the solid material is relatively high, which illustrates the intensity of the hydrogen bonding type interactions. The introduction of methacrylic acid into the system limits the uptake of water from the network. However, the introduction of high function rates strongly polar acid should lead to increased hydrophilicity. This behavior shows that the acid bonds strongly interact within the polymer network and are no longer available for interactions with water molecules in the external environment.

Comparative example C2 and Example 5.

The procedure was as in Example 1, but replacing the BPA30EODMA oligomer with a urethane diacrylate CN965 oligomer from the company CRAY VALLEY. By way of comparison, this same urethane diacrylate was polymerized in the absence of acrylic acid: The compositions and the results are given in Table II below:

TABLE II

Comparative example C3 and examples 6, 7 and 8.

Example 1 was repeated, replacing the BPA30EODMA with PPG 400 DMA in various proportions. The compositions and the results are given in Table III below. BOARD

The results show that stiffening with methacrylic acid takes place even at low levels of methacrylic acid (20%) and that, on the other hand, the presence of propoxy groups allows access to extremely low water recovery rates. .

Comparative example C4 and examples 9 to 11

The procedure is as above, but using for component A a mixture of BPA30EODMA and PPG 400 DMA oigomers.

The compositions as well as the results obtained are given in Table IV below.

TABLE IV

Comparative example C5 and example 12 and 13.

The procedure is as above, but using for component A a mixture of oligomer BPA30EODMA and of dithiomethacrylate W consisting of a mixture of a first component corresponding to formula III (with n 'varying from 1 to 10) and a second component corresponding to the formula:

in a respective first component / second component ratio 65/35. The compositions and the results are indicated in Table V below: TABLE V

Rigidification by methacrylic acid is effective in all cases.

Example 14.

The above examples were reproduced using for component A a mixture of BPA30EODMA and mono-2- (methacryloyloxy) ethyl phthalate (MA phthalate) from the company ALDRICH.

The proportions of the constituents of the composition and the results are shown in Table VI.

TABLE VI

Example 15

As described above, the spherical lenses of power -2 diopters were produced from the composition of Example 2.

The glasses obtained were subjected to an impact resistance test by falling energy increasing ball (increasing the height of fall until rupture).

The results are reported in Table VII below.

TABLE VII

These results show that the compositions according to the invention make it possible to obtain high impact strengths.

Comparative example C6

Example 2 of patent application WO 01/09205 is reproduced to form spherical glasses of power -2 diopters.

The PLEX 6661-0 from CRAY VALLEY has the formula

R ' ₃ and R' denoting, independently of one another, H or CH ₃ .

The glasses obtained, of power -2 diopters and of center thickness 1.1 mm, are subjected to an impact resistance test according to the same protocol as in Example 15. Results:

- number of broken glasses with 520g ball mass 31

- average breaking energy 3300 mJ

Claims

1. Composition which can be polymerized by radical route comprising:

a first component A comprising at least one oligomer carrying at least two radical polymerizable functions and whose homopolymer has a glass transition temperature (Tg) of less than 50 ° C, this component being capable of leading to polymerization a (co) polymer having a glass transition temperature (Tg) equal to or less than 50 ° C, preferably equal or "less than 0 ° G and better 'ranging from -50 ° C to -10 ° Cγ ce- oligomer representing more than 15%, preferably at least 20% of the total weight of the polymerizable monomers present in the composition; and

a second constituent B comprising at least one (meth) acrylic monomer, carrying at least one promoter group of bond H, this (meth) acrylic monomer representing at least 15% of the total weight of the polymerizable monomers and oligomers present in the composition when this monomer is a methacrylic monomer and at least 35% of the total weight of the polymerizable monomers and oligomers present in the composition when this monomer is an acrylic monomer.

2. Composition according to claim 1, characterized in that the oligomer of the first constituent A is a difunctional oligomer.

3. Composition according to claim 2, characterized in that the oligomer is a di (meth) acrylate, preferably a dimethacrylate.

4. Composition according to any one of claims 1 to 3, characterized in that the oligomer has a number-average molar mass M _n from 100 to 5000, preferably 200 to 4000 and better still from 300 to 2000 g. mole ^"

1

5. Composition according to any one of claims 1 to 4, characterized in that the oligomer is chosen from poly (alkylene) glycol di (meth) acrylates, bisphenol-A di (meth) polyethoxylated acrylates, dithio ( meth) acrylates and di (meth) acrylates urethanes.

6. Composition according to any one of the preceding claims, characterized in that the oligomer is chosen from poly (ethylene glycol) dimethacrylates and poly (propylene glycol) dimethacrylates.

7. Composition according to claim 6, characterized in that the oligomer is a poly (propylene glycol) dimethacrylate of average molar mass in number of about 530g. mole ^"1 .

8. Composition according to any one of claims 1 to 3, characterized in that the constituent A further comprises at least one other comonomer, non-oligomer, comprising at least one function which can be polymerized by the radical route.

9. Composition according to Claim 8, characterized in that the radical-polymerizable function is a (meth) acrylate-

10. Composition according to any one of the preceding claims, characterized in that the (meth) acrylic monomer promoting H bonds is a monofunctional monomer.

11. Composition according to one of the preceding claims, characterized in that the (meth) acrylic monomer promoting H bonds corresponds to the formula:

R

I

CH ₂ = CZ-Z '

where R represents H or CH ₃ , Z represents a single covalent bond or a divalent spacer group and Z 'is a promoter group of H bonds.

12. Composition according to claim 11, characterized in that Z is a divalent hydrocarbon chain, optionally interrupted by one or more heteroatoms, preferably chosen from O, S and N, or by one or more groups

carbonyl ç, ester C 0> c _or

O O S by one or more divalent groups chosen from: -NH-CO-NH-,

-NH-COO-,

-NHCOS-,

-NHCSS-.

13. Composition according to claim 12, characterized in that the hydrodarbon chain comprises 1 to 10 carbon atoms, preferably 1 to

6 carbon atoms.

14. Composition according to claim 11, characterized in that Z is a polyether, polyester, polyurethane, polyurea or polyurethane group.

15. Composition according to any one of claims 11 to 14, characterized in that Z 'is chosen from the groups:

COOH, OH, CONHR ',

NHCONHR ", NHCOOR"', NHCOSR ™' and NHR ^V

where R, R ", R '", R ^iv and R ^v

denote, independently of one another, H or a C1-C10 alkyl or Cβ-C10 aryl group.

16. Composition according to claim 15, characterized in that the alkyl group is an aliphatic or cycloaliphatic group.

17. Composition according to claim 16, characterized in that the aliphatic group is -CH ₃ .

18. Composition according to any one of claims 1 1 to 17, characterized in that Z 'is the group -COOH.

19. Composition according to any one of claims 11 to 18, characterized in that R is CH ₃ .

20. Composition according to claim 10, characterized in that the (meth) acrylic monomer promoting H bonds is chosen from acrylic acid, methacrylic acid, mono-2- (methacryloyloxy) ethyl succinate and mono-2 - (methacryloyloxy) ethyl phthalate.

21. Composition according to any one of the preceding claims, characterized in that it further comprises, an effective amount of at least one initiator for thermal and / or photochemical polymerization.

22. Product resulting from the thermal and / or photochemical polymerization of a composition according to any one of claims 1 to 20.

23. Product according to claim 22, characterized in that it has an elastic modulus E 'at 100 ° C of at least 40 MPa, preferably of at least 100 MPa, better still of at least 120 MPa.

24. Product according to any one of claims 21 to 23, characterized in that it consists of an optical glass, in particular, an ophthalmic glass, finished or semi-finished.